Inohydrazide compound, preparation method and application thereof, and plant antibacterial agent

Abstract

The invention relates to the technical field of plant antibacterial agents, in particular to an alkenyl hydrazide compound, a preparation method and application thereof and a plant antibacterial agent. The hydrazide compound disclosed by the invention has an efficient and broad-spectrum inhibition effect on more than ten plant pathogenic fungi, has the advantages of simple structure, easiness in large-scale preparation and no toxicity to animals and plants, and can be used as an effective component or a synergistic component for development and application of a novel green and efficient agricultural antibacterial agent.

Description

Technical Field

[0001] The present invention relates to the technical field of plant antibacterial agents, and particularly relates to an acylhydrazine compound, a preparation method and application thereof, and a plant antibacterial agent. Background Art

[0002] As an important agricultural production material, fungicides play an important role in ensuring food security, the quality of agricultural products, and the safety of the ecological environment. Currently, nearly two hundred fungicide varieties have been commercialized. However, with the long-term and large-scale use of traditional fungicides, the problem of drug resistance has become increasingly prominent. The development of new fungicides is an effective way to solve the above problems. Summary of the Invention

[0003] In view of this, the purpose of the present invention is to provide an acylhydrazine compound, a preparation method and application thereof, and a plant antibacterial agent. The acylhydrazine compound has high-efficiency and broad-spectrum in vitro inhibitory activity against plant pathogens.

[0004] To achieve the above invention purpose, the present invention provides the following technical solutions:

[0005] The present invention provides a structure shown in any one of Formulas 1 to 3:

[0006]

[0007] In Formula 1, R 1 is methyl or n-butyl, and R 2 is methyl or hydrogen;

[0008]

[0009] In Formula 2, -R is mono-substituted or di-substituted in the benzene ring, and the types of R are one or two of fluorine, chlorine, bromine, iodine, trifluoromethyl, methyl, ethyl, isopropyl, and methoxy;

[0010]

[0011] In Formula 3, R is 2-naphthyl.

[0012] Preferably, in Formula 1, R 1 is methyl, and R 2 is methyl; or R 1 is n-butyl, and R 2 is hydrogen;

[0013] In the formula 2, R is 2-fluoro, 3-fluoro, 4-fluoro, 3-chloro, 4-chloro, 3-bromo, 4-bromo, 4-iodo, 3-trifluoromethyl, 4-trifluoromethyl, 2-methyl, 3-methyl, 4-methyl, 4-ethyl, 4-isopropyl, 3-methoxy, 3,4-dimethyl, 3,5-dimethyl, 2,4-difluoro, 2,5-difluoro, 3,4-difluoro, 3,5-difluoro, 2,3-dichloro, 2,4-dichloro, 2,5-dichloro, 3,4-dichloro, 3,5-dichloro, 2-fluoro-4-chloro, 2-fluoro-4-bromo, 2-chloro-4-fluoro or 3-chloro-4-fluoro.

[0014] The present invention also provides a method for preparing the acylhydrazine compounds described in the above technical solution, comprising the following steps:

[0015] Condensing the acrylic acid compound with a hydrazine compound or a hydrochloride salt of a hydrazine compound to obtain the acylhydrazine compound;

[0016] The acrylic acid compound has a structure shown in any one of formulas 4 to 5:

[0017]

[0018] In the formula 4, R 1 is methyl or n-butyl, and R 2 is methyl or hydrogen;

[0019]

[0020] The hydrochloride salt of the hydrazine compound has a structure shown in any one of formulas 6 to 8:

[0021]

[0022]

[0023] In the formula 7, -R is mono-substituted or di-substituted, and the types of R are one or two of fluorine, chlorine, bromine, iodine, trifluoromethyl, methyl, ethyl, isopropyl and methoxy;

[0024]

[0025] In the formula 8, R is 2-naphthyl;

[0026] The hydrazine compound has a structure shown in formulas 9 to 11:

[0027]

[0028] In the formula 10, -R is mono-substituted or di-substituted, and the types of R are one or two of fluorine, chlorine, bromine, iodine, trifluoromethyl, methyl, ethyl, isopropyl and methoxy;

[0029]

[0030] In the formula 11, R is 2-naphthyl.

[0031] Preferably, the molar ratio of the acrylic acid compound to the hydrazine compound or the molar ratio of the acrylic acid compound to the hydrochloride of the hydrazine compound is (1.0 to 1.5):1.0.

[0032] Preferably, the condensation reaction is carried out under the condition of adding a condensing agent;

[0033] The condensing agent includes 1-ethyl-3-dimethylaminopropylcarbodiimide hydrochloride and 1-hydroxybenzotriazole;

[0034] The molar ratio of 1-ethyl-3-dimethylaminopropylcarbodiimide hydrochloride to 1-hydroxybenzotriazole is (1.0 to 1.5):(0.04 to 0.5);

[0035] The molar ratio of the acrylic acid compound to 1-ethyl-3-dimethylaminopropylcarbodiimide hydrochloride is (1.0 to 1.5):(1.0 to 1.5).

[0036] Preferably, the reaction medium of the condensation reaction is an organic solvent;

[0037] The organic solvent is one or more of N,N-dimethylformamide, tetrahydrofuran and acetonitrile.

[0038] Preferably, when the acrylic acid compound and the hydrochloride of the hydrazine compound are subjected to a condensation reaction, the condensation reaction is also carried out under the condition of adding triethylamine;

[0039] The molar ratio of the acrylic acid compound to triethylamine is (1.0 to 1.5):(1.0 to 2.0).

[0040] The present invention also provides the use of the acylhydrazine compound described in the above technical solution, the acylhydrazine compound prepared by the preparation method described in the above technical solution or the acylhydrazine compound represented by formula 12 in plant antibacterial;

[0041]

[0042] In the formula 12, R 1 , R 2 , R 3 and R 4 are all hydrogen;

[0043] or R 1 , R 3 and R 4 are all hydrogen, and R 2 is methyl;

[0044] or R 1 、R 3 and R 4 are all hydrogen, and R 2 is ethyl;

[0045] or R 1 、R 3 and R 4 are all hydrogen, and R 2 is n-propyl;

[0046] or R 1 is methyl, and R 2 、R 3 and R 4 are all hydrogen;

[0047] or R 1 and R 4 are all hydrogen, and R 2 and R 3 are all methyl;

[0048] or R 3 and R 4 are all hydrogen, and R 1 and R 2 are all methyl;

[0049] or R 1 is hydrogen, and R 2 and R 3 are all methyl, and R 4 is 2-chloro or 2-bromo.

[0050] Preferably, the pathogenic bacteria in the plant antibacterial agent include Fusarium oxysporum f. sp. vasinfectum, Fusarium oxysporum f. sp. niveum, Fusarium coeruleum, Gibberella zeae, Alternaria solani, Alternaria brassicae, Alternaria alternata, Curvularia lunata, Colletotrichum gloeosporioides, Fusarium oxysporum f. sp. cucumerinum, Valsa mali, Magnaporthe oryzae, Physalospora piricola, Sphaerotheca fuliginea, or Plasmopara viticola.

[0051] The present invention also provides a plant antibacterial agent, which includes the acylhydrazine compounds described in the above technical solution, the acylhydrazine compounds prepared by the preparation method described in the above technical solution, or the acylhydrazine compounds shown by Formula 12.

[0052] The present invention provides a structure shown by any one of Formulas 1 to 3:

[0053]

[0054] In Formula 1, R 1 is methyl or n-butyl, and R 2 is methyl or hydrogen;

[0055]

[0056] In the formula 2, -R is mono-substituted or di-substituted in the benzene ring, and the type of R is one or two of fluorine, chlorine, bromine, iodine, trifluoromethyl, methyl, ethyl, isopropyl and methoxy;

[0057]

[0058] In the formula 3, R is 2-naphthyl.

[0059] The hydrazide compounds of the present invention play a highly efficient and broad-spectrum inhibitory effect on more than a dozen plant pathogenic fungi by inhibiting succinate dehydrogenase and destroying the cell membrane structure, and have the advantages of simple structure, easy large-scale preparation and non-toxicity to animals and plants, and can be used as an active ingredient or a synergistic ingredient for the development and application of new green and highly efficient agricultural antibacterial agents. Detailed implementation mode

[0060] The present invention provides a structure shown in any one of formulas 1 to 3:

[0061]

[0062] In the formula 1, R 1 is methyl or n-butyl, and R 2 is methyl or hydrogen;

[0063]

[0064] In the formula 2, -R is mono-substituted or di-substituted in the benzene ring, and the type of R is one or two of fluorine, chlorine, bromine, iodine, trifluoromethyl, methyl, ethyl, isopropyl and methoxy;

[0065]

[0066] In the formula 3, R is 2-naphthyl.

[0067] In the present invention, in the formula 1, R 1 is specifically methyl, and R 2 is specifically methyl;

[0068] Or R 1 is specifically n-butyl, and R 2 is specifically hydrogen.

[0069] In the present invention, in Formula 2, R is specifically 2-fluoro, 3-fluoro, 4-fluoro, 3-chloro, 4-chloro, 3-bromo, 4-bromo, 4-iodo, 3-trifluoromethyl, 4-trifluoromethyl, 2-methyl, 3-methyl, 4-methyl, 4-ethyl, 4-isopropyl, 3-methoxy, 3,4-dimethyl, 3,5-dimethyl, 2,4-difluoro, 2,5-difluoro, 2,4-difluoro, 2,5-difluoro, 3,4-difluoro, 3,5-difluoro, 2,3-dichloro, 2,4-dichloro, 2,5-dichloro, 3,4-dichloro, 3,5-dichloro, 2-fluoro-4-chloro, 2-fluoro-4-bromo, 2-chloro-4-fluoro or 3-chloro-4-fluoro.

[0070] The present invention also provides a method for preparing the acylhydrazine compounds described in the above technical solution, comprising the following steps:

[0071] Performing a condensation reaction on an acrylic acid compound and a hydrazine compound or a hydrochloride salt of a hydrazine compound to obtain the acylhydrazine compound;

[0072] The acrylic acid compound has a structure shown in any one of Formulas 4 to 5:

[0073]

[0074] In Formula 4, R 1 is methyl or n-butyl, and R 2 is methyl or hydrogen;

[0075]

[0076] The hydrochloride salt of the hydrazine compound has a structure shown in any one of Formulas 6 to 8:

[0077]

[0078] In Formula 7, -R is mono-substituted or di-substituted, and the types of R are one or two of fluorine, chlorine, bromine, iodine, trifluoromethyl, methyl, ethyl, isopropyl and methoxy;

[0079]

[0080] In Formula 8, R is 2-naphthyl;

[0081] The hydrazine compound has a structure shown in Formulas 9 to 11:

[0082]

[0083] In Formula 10, -R is mono-substituted or di-substituted, and the types of R are one or two of fluorine, chlorine, bromine, iodine, trifluoromethyl, methyl, ethyl, isopropyl and methoxy;

[0084]

[0085] In the formula 11, R is 2-naphthyl.

[0086] In the present invention, the molar ratio of the acrylic acid compound to the hydrazine compound or the molar ratio of the acrylic acid compound to the hydrochloride of the hydrazine compound is preferably (1.0 to 1.5):1.0, more preferably (1.2 to 1.4):1.0. In the examples of the present invention, the molar ratio of the acrylic acid compound to the hydrazine compound or the molar ratio of the acrylic acid compound to the hydrochloride of the hydrazine compound can be 1.2:1.

[0087] In the present invention, the condensation reaction is preferably carried out under the condition of adding a condensing agent; the condensing agent preferably includes 1-ethyl-3-dimethylaminopropylcarbodiimide hydrochloride (EDCI) and 1-hydroxybenzotriazole (HOBT); the molar ratio of 1-ethyl-3-dimethylaminopropylcarbodiimide hydrochloride to 1-hydroxybenzotriazole is preferably (1.0 to 1.5):(0.04 to 0.5), more preferably (1.2 to 1.4):(0.05 to 0.1). In the examples of the present invention, the molar ratio of 1-ethyl-3-dimethylaminopropylcarbodiimide hydrochloride to 1-hydroxybenzotriazole can be 1.2:0.1 or 1.2:0.05.

[0088] In the present invention, the molar ratio of the acrylic acid compound to 1-ethyl-3-dimethylaminopropylcarbodiimide hydrochloride is preferably (1.0 to 1.5):(1.0 to 1.5). In the examples of the present invention, the molar ratio of the acrylic acid compound to 1-ethyl-3-dimethylaminopropylcarbodiimide hydrochloride can be 1:1.

[0089] In the present invention, the reaction medium of the condensation reaction is preferably an organic solvent; the organic solvent is preferably one or more of N,N-dimethylformamide, tetrahydrofuran and acetonitrile, more preferably tetrahydrofuran or N,N-dimethylformamide. When the organic solvent is two or more of the above specific selections, the present invention has no special limitation on the ratio of the above specific substances, and they can be mixed in any ratio.

[0090] In the present invention, the dosage ratio of the hydrazine compound to the solvent is preferably 5 mmol:(20 to 30) mL. In the examples of the present invention, the dosage ratio of the hydrazine compound to the solvent can be 5 mmol:20 mL or 5 mmol:30 mL.

[0091] In the present invention, when a condensation reaction is carried out between an acrylic acid compound and a hydrochloride salt of a hydrazine compound, the condensation reaction is preferably carried out under the condition of adding triethylamine; the molar ratio of the acrylic acid compound to triethylamine is preferably (1.0 - 1.5):(1.0 - 2.0).

[0092] In the present invention, the temperature of the condensation reaction is preferably 10 - 50 °C, and the time is preferably 2 h.

[0093] In the present invention, the process of the condensation reaction preferably includes the following steps:

[0094] After dissolving the hydrazine compound in a solvent, under the conditions of an ice-water bath and stirring, EDCI, HOBT and the acrylic acid compound are added in sequence, and then stirred at room temperature until the reaction is complete, followed by concentration under reduced pressure.

[0095] The present invention has no special limitation on the processes of the ice-water bath, stirring and concentration under reduced pressure, and those well-known to those skilled in the art can be used.

[0096] Or the process of the condensation reaction preferably includes the following steps:

[0097] After mixing the acrylic acid compound, EDCI, HOBT and the solvent, stir until all the solids are dissolved, cool the resulting mixture to 0 °C, add the hydrochloride salt of the hydrazine compound and triethylamine, and stir at room temperature for 8 h until the reaction is complete.

[0098] The present invention has no special limitation on the stirring process, and those well-known to those skilled in the art can be used.

[0099] After the condensation reaction is completed, the present invention preferably further includes adding water, extracting with ethyl acetate, washing the organic phase successively with water and saturated brine, drying with anhydrous sodium sulfate, filtering, concentrating the filtrate to dryness under reduced pressure, and subjecting the obtained residue to silica gel column chromatography separation or recrystallization with a mixed solvent of petroleum ether and ethyl acetate.

[0100] The present invention also provides the application of the acylhydrazine compounds described in the above technical solution, the acylhydrazine compounds prepared by the preparation method described in the above technical solution, or the acylhydrazine compounds represented by formula 12 in plant antibacterial;

[0101]

[0102] In formula 12, R 1 、R 2 、R 3 and R 4 are all hydrogen;

[0103] Or R 1 、R 3 and R4 All are hydrogen, R 2 is methyl;

[0104] or R 1 , R 3 and R 4 All are hydrogen, R 2 is ethyl;

[0105] or R 1 , R 3 and R 4 All are hydrogen, R 2 is n-propyl;

[0106] or R 1 is methyl, R 2 , R 3 and R 4 All are hydrogen;

[0107] or R 1 and R 4 All are hydrogen, R 2 and R 3 All are methyl;

[0108] or R 3 and R 4 All are hydrogen, R 1 and R 2 All are methyl;

[0109] or R 1 is hydrogen, R 2 and R 3 All are methyl, R 4 is 2-chloro or 2-bromo.

[0110] In the present invention, the pathogenic bacteria in the plant antibacterial preferably include Fusarium oxysporum f. sp. vasinfectum, Fusarium oxysporum f. sp. niveum, Fusarium coeruleum, Gibberella zeae, Alternaria solani, Alternaria brassicae, Alternaria alternata, Curvularia lunata, Colletotrichum gloeosporioides, Fusarium oxysporum f. sp. cucumerinum, Valsa mali, Magnaporthe oryzae, Physalospora piricola, Sphaerotheca fuliginea or Plasmopara viticola.

[0111] The present invention also provides a plant antibacterial agent, including the acylhydrazine compounds described in the above technical solution, the acylhydrazine compounds prepared by the preparation method described in the above technical solution or the acylhydrazine compounds shown in Formula 12. In the present invention, the mass percentage content of the acylhydrazine compounds in the plant antibacterial agent is preferably 200 - 500 mg / L, more preferably 400 mg / L.

[0112] In the present invention, the plant antibacterial agent preferably further comprises a plant antibacterial drug; the present invention does not impose any special limitations on the type and dosage of the plant antibacterial drug, and those well-known to those skilled in the art can be adopted.

[0113] Next, the technical solutions in the present invention will be clearly and completely described in conjunction with the embodiments in the present invention. Obviously, the described embodiments are only a part of the embodiments of the present invention, rather than all the embodiments. All other embodiments obtained by those of ordinary skill in the art based on the embodiments in the present invention without making creative efforts belong to the scope of protection of the present invention.

[0114] Examples 1-8

[0115] The structural formula of the acylhydrazine compound is

[0116]

[0117] Among them, R 1 , R 2 , R 3 and R 4 are shown in Table 1:

[0118] Table 1 Types of R 1 , R 2 , R 3 and R 4 in Examples 1-8

[0119] Example <![CDATA[R 1 > <![CDATA[R 2 > <![CDATA[R 3 > <![CDATA[R 4 > Example 1 Hydrogen Hydrogen Hydrogen Hydrogen Example 2 Hydrogen Methyl Hydrogen Hydrogen Example 3 Hydrogen Ethyl Hydrogen Hydrogen Example 4 Hydrogen n-Propyl Hydrogen Hydrogen Example 5 Methyl Hydrogen Hydrogen Hydrogen Example 6 Hydrogen Methyl Methyl Hydrogen Example 7 Methyl Methyl Hydrogen Hydrogen Example 8 Hydrogen Methyl Methyl 2-Chloro

[0120] Preparation methods of the compounds corresponding to Examples 1-8:

[0121] In a reaction flask, dissolve phenylhydrazine or substituted phenylhydrazine (5 mmol) in anhydrous tetrahydrofuran (30 mL). Under the conditions of cooling in an ice-water bath and stirring, sequentially add EDCl (6 mmol), HOBT (0.5 mmol) and acrylic acid (6 mmol), then stir at room temperature until the reaction is complete. Concentrate under reduced pressure, add about 50 mL of water to the residue, extract with ethyl acetate, wash the organic phase successively with water and saturated brine, then dry with anhydrous sodium sulfate, filter, concentrate the obtained filtrate to dryness under reduced pressure, and recrystallize the obtained residue with a mixed solvent of petroleum ether and ethyl acetate with a volume ratio of 3:1 to obtain the acylhydrazine compound;

[0122] Among them, the structural formula of phenylhydrazine or substituted phenylhydrazine is wherein the type of R 4 corresponds to the acylhydrazine compounds in Examples 1-8;

[0123] The structural formula of acrylic acid is Wherein R 1 , R 2 and R 3 are of the same types as the acylhydrazine compounds of Examples 1 to 8;

[0124] The physical and chemical properties and nuclear magnetic resonance spectrum data of Examples 1 to 8 are as follows:

[0125] Example 1, chemical name: N'-phenylacryloylhydrazine (denoted as Compound 1): white powder, yield 83%, melting point 174.1 - 174.6 °C; 1 H NMR (400 MHz, DMSO-d6) δ 9.92 (d, Hz, 1H), 7.83 (d, 1H), 7.15 (dd, 2H), 6.74 - 6.69 (m, 3H), 6.33 (dd, 1H), 6.19 (dd, 1H), 5.71 (dd, 1H);

[0126] Example 2, chemical name: N'-phenylcrotonoylhydrazine (denoted as Compound 2): white powder, yield 88%, melting point 145.4 - 146.2 °C; 1 H NMR (400 MHz, DMSO-d6) δ 9.70 (d, J = 3.1 Hz, 1H), 7.75 (d, J = 3.0 Hz, 1H), 7.16 - 7.10 (m, 2H), 6.75 - 6.66 (m, 4H), 6.00 (dd, J = 15.4, 1.8 Hz, 1H), 1.83 (dd, J = 6.8, 1.7 Hz, 3H);

[0127] Example 3, chemical name: trans-N'-phenyl-2-pentenoylhydrazine (denoted as Compound 3): white powder, yield 84%, melting point 160.2 - 160.7 °C; 1 H NMR (400 MHz, DMSO-d6) δ 9.72 (d, 1H), 7.76 (d, 1H), 7.13 (dd, 2H), 6.78 (dt, 1H), 6.72 - 6.68 (m, 3H), 5.99 (dt, 1H), 2.25 - 2.16 (m, 2H), 1.03 (t, 3H);

[0128] Example 4, chemical name: trans-N'-phenyl-2-hexenoylhydrazine (denoted as Compound 4): bright yellow powder, yield 88%, melting point 165.5 - 167.4 °C; 1 H NMR (400 MHz, DMSO-d6) δ 9.72 (d, 1H), 7.76 (d, Hz, 1H), 7.16 - 7.11 (m, 2H), 6.73 - 6.67 (m, 4H), 6.00 (d, 1H), 2.16 (qd, 2H), 1.45 (h, 2H), 0.91 (t, 3H);

[0129] Example 5, with the chemical name of trans-N'-phenyl-2-heptenohydrazide (denoted as Compound 5): white powder, yield 81%, melting point 152.6 - 153.4 °C; 1 H NMR (400 MHz, DMSO-d6) δ 9.71 (d, 1H), 7.76 (d, 1H), 7.14 (t, J = 7.8 Hz, 2H), 6.74 - 6.67 (m, 4H), 6.00 (dt, 1H), 2.18 (m, 2H), 1.45 - 1.37 (m, 2H), 1.32 (m, 2H), 0.90 (t, 3H);

[0130] Example 6, with the chemical name of N'-phenylmethacryloylhydrazide (denoted as Compound 6): white powder, yield 80%, melting point 148.7 - 149.9 °C; 1 H NMR (400 MHz, DMSO-d6) δ 9.84 (d, 1H), 7.71 (d, 1H), 7.17 - 7.10 (m, 2H), 6.75 - 6.67 (m, 3H), 5.78 (t, 1H), 5.43 (t, 1H), 1.91 (t, 3H);

[0131] Example 7, with the chemical name of N'-phenyltigloylhydrazide (denoted as Compound 7): white powder, yield 85%, melting point 96.5 - 97.8 °C; 1 H NMR (400 MHz, DMSO-d6) δ 9.66 (s, 1H), 7.65 (s, 1H), 7.12 (dd, 2H), 6.76 - 6.65 (m, 3H), 6.44 (m, 1H), 1.80 (s, 3H), 1.73 (dd, 3H);

[0132] Example 8, with the chemical name of N'-phenyl-3-methyl-2-butenohydrazide (denoted as Compound 8): white powder, yield 78%, melting point 103.8 - 104.5 °C; 1 H NMR (400 MHz, DMSO-d6) δ 9.55 (d, 1H), 7.66 (d, 1H), 7.13 (dd, 2H), 6.72 - 6.67 (m, 3H), 5.75 (p, 1H), 2.09 (d, 3H), 1.84 (d, 3H).

[0133] Examples 9 - 40

[0134] The structural formula of the enoylhydrazide compounds is

[0135]

[0136] Among them, the types of R are shown in Table 2:

[0137] Table 2 Types of R in Examples 9 - 40

[0138] Example R Example R Example R Example R Example 9 2-F Example 17 4-I Example 25 <![CDATA[3-OCH3]]> Example 33 2,4-2Cl Example 10 3-F Example 18 <![CDATA[3-CF3]]> Example 26 <![CDATA[3,4-2CH3]]> Example 34 2,5-2Cl Example 11 4-F Example 19 <![CDATA[4-CF3]]> Example 27 <![CDATA[3,5-2CH3]]> Example 35 3,4-2Cl Example 12 2-Cl Example 20 <![CDATA[2-CH3]]> Example 28 2,4-2F Example 36 3,5-2Cl Example 13 3-Cl Example 21 <![CDATA[3-CH3]]> Example 29 2,5-2F Example 37 2F-4Cl Example 14 4-Cl Example 22 <![CDATA[4-CH3]]> Example 30 3,4-2F Example 38 2F-4Br Example 15 3-Br Example 23 4-Et Example 31 3,5-2F Example 39 2Cl-4F Example 16 4-Br Example 24 4-iPr Example 32 2.3-2Cl Example 40 3Cl-4F

[0139] Preparation methods of the compounds corresponding to Examples 9 - 40:

[0140] In a reaction flask, dissolve phenylhydrazine or substituted phenylhydrazine (5 mmol) in anhydrous tetrahydrofuran (30 mL). Under the conditions of cooling in an ice - water bath and stirring, successively add EDCl (6 mmol), HOBT (0.5 mmol), and acrylic acid (6 mmol). Then stir at room temperature until the reaction is complete. Concentrate under reduced pressure. Add about 50 mL of water to the residue, extract with ethyl acetate. Wash the organic phase successively with water and saturated brine, then dry with anhydrous sodium sulfate, filter. Concentrate the obtained filtrate to dryness under reduced pressure. Recrystallize the obtained residue with a mixed solvent of petroleum ether and ethyl acetate with a volume ratio of 3:1 to obtain the enoylhydrazine compounds;

[0141] Among them, the structural formula of phenylhydrazine or substituted phenylhydrazine is The type of R therein corresponds to R in the enoylhydrazine compounds of Examples 9 - 40;

[0142] The structural formula of acrylic acid is

[0143] The physical and chemical properties and NMR spectral data of Examples 9 - 40 are as follows:

[0144] Example 9, chemical name: N'-(2 - fluorophenyl) isopentenoylhydrazine (denoted as Compound 9): white solid, yield 88%, melting point 104.5 - 105.3 °C; 1 HNMR(400MHz,DMSO - d6)δ9.63(d,J = 2.7Hz,2H),7.57(s,1H),7.06(ddd,2H),7.00 - 6.95(m,1H),6.74 - 6.68(m,3H),5.76 - 5.74(m,2H),1.84(d,6H);

[0145] Example 10, chemical name: N'-(3 - fluorophenyl) isopentenoylhydrazine (denoted as Compound 10): white powder, yield 88%, melting point 90.5 - 91.3 °C; 1 HNMR(400MHz,DMSO - d6)δ9.60(d,1H),7.99(d,1H),7.20 - 7.08(m,1H),6.51(dd,1H),6.45(td,1H),6.39(dt,1H),2.09(d,3H),1.84(d,3H);

[0146] Example 11, chemical name: N'-(4-fluorophenyl)isopentenoyl hydrazide (denoted as Compound 11): bright yellow powder, yield 88%, melting point 91.3 - 92.2 °C; 1 HNMR(400MHz,DMSO-d6)δ9.58(d,1H),7.64(d,1H),6.97(t,2H),6.73 - 6.61(m,2H),5.76 - 5.70(m,1H),2.08(d,3H),1.83(d,3H);

[0147] Example 12, chemical name: N'-(2-chlorophenyl)isopentenoyl hydrazide (denoted as Compound 12): white powder, yield 85%, melting point 88.9 - 91.4 °C; 1 HNMR(400MHz,DMSO-d6)δ9.75(d,1H),7.37(d,1H),7.28(dd,1H),7.15(td,1H),6.80 - 6.68(m,2H),5.77(s,1H),2.09(d,3H),1.85(d,3H);

[0148] Example 13, chemical name: N'-(3-chlorophenyl)isopentenoyl hydrazide (denoted as Compound 13): bright yellow powder, yield 67%, melting point 89.5 - 90.1 °C; 1 H NMR(400MHz,DMSO-d6)δ9.63(d,1H),8.01(d,1H),7.14(t,J = 8.0Hz,1H),6.73 - 6.69(m,1H),6.68 - 6.63(m,1H),5.76(s,1H),2.10(d,3H),1.85(d,3H);

[0149] Example 14, chemical name: N'-(4-chlorophenyl)isopentenoyl hydrazide (denoted as Compound 14): bright yellow powder, yield 67%, melting point 98.2 - 99.3 °C; 1 H NMR(400MHz,DMSO-d6)δ9.60(s,1H),7.87(s,1H),7.24 - 7.10(m,2H),6.73 - 6.64(m,2H),5.76 - 5.71(m,1H),2.08(d,3H),1.83(d,3H);

[0150] Example 15, chemical name: N'-(3-bromophenyl)isopentenoyl hydrazide (denoted as Compound 15): yellow powder, yield 65%, melting point 103.5 - 104.5 °C; 11H NMR (400 MHz, DMSO-d6) δ 8.03 (d, 1H), 7.12 (t, 1H), 6.91 - 6.81 (m, 1H), 6.73 (dd, 1H), 5.81 - 5.76 (m, 1H), 2.14 (d, 3H), 1.88 (d, 3H);

[0151] Example 16, chemical name N'-(4-bromophenyl)isopentenoyl hydrazide (denoted as Compound 16): yellow powder, yield 71%, melting point 104.3 - 104.8 °C; 1 1H NMR (400 MHz, DMSO-d6) δ 9.60 (s, 1H), 7.88 (s, 1H), 7.36 - 7.23 (m, 2H), 6.68 - 6.59 (m, 2H), 5.76 - 5.70 (m, 1H), 2.08 (d, 3H), 1.83 (d, 3H);

[0152] Example 17, chemical name N'-(4-iodophenyl)isopentenoyl hydrazide (denoted as Compound 17): bright yellow powder, yield 75%, melting point 123.1 - 123.7 °C; 1 1H NMR (400 MHz, DMSO-d6) δ 9.58 (s, 1H), 7.87 (s, 1H), 7.42 (d, 2H), 6.53 (d, 2H), 5.73 (t, 1H), 2.08 (d, 3H), 1.83 (d, 3H);

[0153] Example 18, chemical name N'-(3-trifluoromethylphenyl)isopentenoyl hydrazide (denoted as Compound 18): bright yellow powder, yield 74%, melting point 105.2 - 105.9 °C; 1 1H NMR (400 MHz, DMSO-d6) δ 9.69 (s, 1H), 8.17 (s, 1H), 7.35 (t, 1H), 7.03 - 6.89 (m, 3H), 5.79 - 5.73 (m, 1H), 2.09 (d, 3H), 1.85 (d, 3H);

[0154] Example 19, chemical name N'-(4-trifluoromethylphenyl)isopentenoyl hydrazide (denoted as Compound 19): bright yellow powder, yield 77%, melting point 144.4 - 145.2 °C; 1 1H NMR (400 MHz, DMSO-d6) δ 9.71 (d, 1H), 8.35 (d, 1H), 7.46 (d, 2H), 6.78 (d, 2H), 5.79 - 5.74 (m, 1H), 2.10 (d, 3H), 1.85 (d, 3H);

[0155] Example 20, with the chemical name N'-(2-methylphenyl)isopentenoyl hydrazide (denoted as Compound 20): bright yellow powder, yield 82%, melting point 115.1 - 115.8 °C; 1 HNMR (400 MHz, DMSO-d6) δ 9.61 (d, 1H), 7.07 - 6.96 (m, 3H), 6.70 - 6.56 (m, 2H), 5.80 - 5.74 (m, 1H), 2.15 (s, 3H), 2.10 (d, 3H), 1.84 (d, 3H);

[0156] Example 21, with the chemical name N'-(3-methylphenyl)isopentenoyl hydrazide (denoted as Compound 21): bright yellow powder, yield 72%, melting point 73.8 - 74.6 °C; 1 H NMR (400 MHz, DMSO-d6) δ 9.61 (d, 1H), 7.07 - 6.96 (m, 3H), 6.70 - 6.56 (m, 2H), 5.80 - 5.74 (m, 1H), 2.15 (s, 3H), 2.10 (d, 3H), 1.84 (d, 3H);

[0157] Example 22, with the chemical name N'-(4-methylphenyl)isopentenoyl hydrazide (denoted as Compound 22): bright yellow powder, yield 80%, melting point 79.5 - 80.3 °C; 1 HNMR (400 MHz, DMSO-d6) δ 9.53 (s, 1H), 7.49 (s, 1H), 6.93 (d, 1H), 6.60 (d, 1H), 5.73 (dd, 1H), 2.17 (d, 3H), 2.08 (d, 2H), 1.82 (d, 2H);

[0158] Example 23, with the chemical name N'-(4-ethylphenyl)isopentenoyl hydrazide (denoted as Compound 23): white powder, yield 77%, melting point 85.3 - 86.1 °C; 1 H NMR (400 MHz, DMSO-d6) δ 9.53 (d, 1H), 7.48 (d, 1H), 6.96 (d, J = 8.4 Hz, 2H), 6.63 (d, 2H), 5.74 (q, 1H), 2.08 (d, 3H), 1.82 (d, 3H), 1.11 (t, 3H);

[0159] Example 24, with the chemical name N'-(4-isopropylphenyl)isopentenoyl hydrazide (denoted as Compound 24): white powder, yield 74%, melting point 100.2 - 100.7 °C; 1HNMR(400MHz, DMSO-d6) δ 9.53 (d, 1H), 7.47 (d, 1H), 6.99 (d, J = 8.5Hz, 2H), 6.63 (d, 2H), 5.73 (t, 1H), 2.08 (d, 3H), 1.82 (d, 3H), 1.14 (d, 6H);

[0160] Example 25, chemical name: N'-(3-methoxyphenyl)isopentenyl hydrazide (denoted as Compound 25): yellowish-brown powder, yield 59%, melting point 75.9 - 76.7 °C; 1 HNMR(400MHz, DMSO-d6) δ 9.53 (d, 1H), 7.65 (d, 1H), 7.02 (t, 1H), 6.34 - 6.18 (m, 2H), 3.67 (s, 3H), 2.08 (d, 3H), 1.83 (d, 3H);

[0161] Example 26, chemical name: N'-(3,4-dimethylphenyl)isopentenyl hydrazide (denoted as Compound 26): light yellow powder, yield 85%, melting point 71.2 - 72 °C; 1 HNMR(400MHz, DMSO) δ 9.51 (d, J = 3.6Hz, 1H), 7.39 (d, J = 3.5Hz, 1H), 6.87 (d, J = 8.1Hz, 1H), 6.51 (d, J = 2.4Hz, 1H), 6.43 (dd, J = 8.0, 2.5Hz, 1H), 5.76 - 5.70 (m, 1H), 2.11 (s, 3H), 2.08 (d, J = 1.3Hz, 6H), 1.82 (d, J = 1.3Hz, 3H);

[0162] Example 27, chemical name: N'-(3,5-dimethylphenyl)isopentenyl hydrazide (denoted as Compound 27): white powder, yield 86.2%, melting point 90.5 - 91.2 °C; 1 HNMR(400MHz, DMSO) δ 9.49 (d, J = 3.3Hz, 1H), 7.46 (d, J = 3.2Hz, 1H), 6.32 (d, J = 9.2Hz, 3H), 5.76 - 5.70 (m, 1H), 2.15 (s, 6H), 2.08 (d, J = 1.3Hz, 3H), 1.83 (d, J = 1.3Hz, 3H);

[0163] Example 28, chemical name: N'-(2,4-difluorophenyl)isopentenyl hydrazide (denoted as Compound 28): white powder, yield 81%, melting point 74.1 - 74.8 °C; 11H NMR (400 MHz, DMSO-d6) δ 9.63 (d, 1H), 7.50 (s, 1H), 7.12 (ddd, 1H), 6.96 - 6.83 (m, 1H), 6.72 (td, 1H), 5.77 - 5.71 (m, 1H), 2.08 (d, 3H), 1.83 (d, 3H);

[0164] Example 29, chemical name: N'-(2,5-difluorophenyl)isopentenoyl hydrazide (denoted as Compound 29): white powder, yield 91.2%, melting point 73.5 - 74.1 °C; 1 1H NMR (400 MHz, DMSO) δ 9.65 (d, J = 2.8 Hz, 1H), 7.52 (s, 0H), 7.13 (ddd, J = 11.8, 8.9, 2.8 Hz, 1H), 6.89 (td, J = 8.7, 1.5 Hz, 1H), 6.72 (td, J = 9.4, 5.8 Hz, 1H), 5.77 - 5.71 (m, 1H), 2.09 (d, J = 1.3 Hz, 3H), 1.83 (d, J = 1.3 Hz, 3H);

[0165] Example 30, chemical name: N'-(3,4-difluorophenyl)isopentenoyl hydrazide (denoted as Compound 30): white powder, yield 75%, melting point 106.2 - 106.7 °C; 1 1H NMR (400 MHz, DMSO-d6) δ 9.61 (d, 1H), 7.90 (d, 1H), 7.18 (dt, 1H), 6.60 (ddd, 1H), 6.53 - 6.43 (m, 1H), 5.76 - 5.71 (m, 1H), 2.09 (d, 3H), 1.84 (d, 3H);

[0166] Example 31, chemical name: N'-(3,5-difluorophenyl)isopentenoyl hydrazide (denoted as Compound 31): light yellow powder, 92%, melting point 79.2 - 80.2 °C; 1 1H NMR (400 MHz, DMSO) δ 9.65 (s, 1H), 7.91 (s, 1H), 7.09 (ddd, J = 11.4, 8.8, 5.0 Hz, 1H), 6.45 (m, J = 22.6, 10.3, 6.7, 3.2 Hz, 2H), 5.79 - 5.73 (m, 1H), 2.10 (d, J = 1.4 Hz, 3H), 1.85 (d, J = 1.4 Hz, 3H);

[0167] Example 32, chemical name: N'-(2,3-dichlorophenyl)isopentenoyl hydrazide (denoted as Compound 32): light yellow solid, melting point 134.1 - 134.9 °C; 1HNMR(400MHz, DMSO) δ 9.66 (s, 1H), 7.34 (d, J = 8.8 Hz, 1H), 6.82 (d, J = 2.6 Hz, 1H), 6.67 (dd, J = 8.7, 2.7 Hz, 1H), 5.77 - 5.71 (m, 1H), 2.09 (s, 3H), 1.84 (s, 3H);

[0168] Example 33, with the chemical name N'-(2,4-dichlorophenyl)isopentenoyl hydrazide (denoted as Compound 33): a white solid, melting point 98.8 - 99.2 °C; 1 HNMR(400MHz, DMSO) δ 9.75 (s, 1H), 7.56 (s, 1H), 7.40 (d, J = 2.4 Hz, 1H), 7.21 (dd, J = 8.8, 2.4 Hz, 1H), 6.69 (d, J = 8.8 Hz, 1H), 5.79 - 5.73 (m, 1H), 2.09 (d, J = 1.3 Hz, 3H), 1.85 (d, J = 1.3 Hz, 3H);

[0169] Example 34, with the chemical name N'-(2,5-dichlorophenyl)isopentenoyl hydrazide (denoted as Compound 34): a light yellow powder, yield 75%, melting point 117.8 - 118.6 °C; 1 HNMR(400MHz, DMSO-d6) δ 9.83 (d, 1H), 7.30 (d, 2H), 7.13 (d, 1H), 6.90 (t, 1H), 5.73 - 5.68 (m, 1H), 2.04 (d, 3H), 1.80 (d, 3H);

[0170] Example 35, with the chemical name N'-(3,4-dichlorophenyl)isopentenoyl hydrazide (denoted as Compound 35): a light yellow powder, yield 79%, melting point 109.4 - 110.2 °C; 1 HNMR(400MHz, DMSO-d6) δ 9.66 (s, 1H), 7.34 (d, 1H), 6.82 (d, 1H), 6.67 (dd, 1H), 5.77 - 5.71 (m, 1H), 2.09 (s, 3H), 1.84 (s, 3H);

[0171] Example 36, with the chemical name N'-(3,5-dichlorophenyl)isopentenoyl hydrazide (denoted as Compound 36): a white solid, melting point 130.9 - 131.5 °C; 11H NMR (400 MHz, DMSO) δ 9.75 (s, 1H), 7.73 (s, 1H), 7.31 (d, J = 8.4 Hz, 1H), 6.77 (dd, J = 8.4, 2.5 Hz, 1H), 6.64 (d, J = 2.5 Hz, 1H), 5.77 (t, J = 1.4 Hz, 1H), 2.10 (d, J = 1.3 Hz, 3H), 1.86 (d, J = 1.3 Hz, 3H);

[0172] Example 37, chemical name N'-(2-fluoro-4-chlorophenyl)isopentenoyl hydrazide (denoted as Compound 37): brown powder, melting point 98.3 - 99.2 °C; 1 1H NMR (400 MHz, DMSO) δ 9.65 (d, J = 2.4 Hz, 1H), 7.76 (d, J = 2.4 Hz, 1H), 7.25 (dd, J = 11.5, 2.4 Hz, 1H), 7.06 (d, J = 8.6 Hz, 1H), 6.70 (t, J = 9.1 Hz, 1H), 5.74 (t, J = 1.4 Hz, 1H), 2.09 (d, J = 1.4 Hz, 3H), 1.84 (d, J = 1.4 Hz, 3H);

[0173] Example 38, chemical name N'-(2-fluoro-4-bromophenyl)isopentenoyl hydrazide (denoted as Compound 38): light yellow powder, melting point 94.2 - 92 °C; 1 1H NMR (400 MHz, DMSO) δ 9.65 (d, J = 2.3 Hz, 1H), 7.35 (dd, J = 11.3, 2.2 Hz, 1H), 7.17 (d, J = 8.4 Hz, 0H), 6.66 (t, J = 9.0 Hz, 1H), 5.74 (t, J = 1.4 Hz, 1H), 2.09 (d, J = 1.3 Hz, 3H), 1.84 (d, J = 1.3 Hz, 3H);

[0174] Example 39, chemical name N'-(4-fluoro-2-chlorophenyl)isopentenoyl hydrazide (denoted as Compound 39): light yellow powder, yield 78%, melting point 80.7 - 81.6 °C; 1 1H NMR (400 MHz, DMSO-d6) δ 9.76 (d, 1H), 7.35 - 7.24 (m, 2H), 7.05 (td, 1H), 6.72 (dd, 1H), 5.79 - 5.73 (m, 1H), 2.09 (d, 3H), 1.84 (d, 3H);

[0175] Example 40, chemical name N'-(4-fluoro-3-chlorophenyl)isopentenoyl hydrazide (denoted as Compound 40): white powder, yield 88%, melting point 116.7 - 117.5 °C;1 1H NMR (400 MHz, DMSO-d6) δ 9.65 (d, 1H), 7.92 (d, 1H), 7.18 (t, J = 9.1 Hz, 1H), 6.77 (dd, 1H), 6.73 - 6.61 (m, 1H), 5.77 - 5.72 (m, 1H), 2.09 (d, 3H), 1.84 (d, 3H).

[0176] Example 41

[0177] The structural formula of the acylhydrazine compound is

[0178]

[0179] wherein, the type of R is 2-naphthyl;

[0180] The preparation method of the compound corresponding to Example 41:

[0181] In a reaction flask, dissolve 2-naphthylhydrazine (5 mmol) in anhydrous tetrahydrofuran (30 mL). Under the conditions of ice-water bath cooling and stirring, sequentially add EDCl (6 mmol), HOBT (0.5 mmol) and acrylic acid (6 mmol), then stir at room temperature until the reaction is complete. Concentrate under reduced pressure, add about 50 mL of water to the residue, extract with ethyl acetate, wash the organic phase successively with water and saturated brine, then dry with anhydrous sodium sulfate, filter, concentrate the obtained filtrate to dryness under reduced pressure, and recrystallize the obtained residue with a mixed solvent of petroleum ether and ethyl acetate with a volume ratio of 3:1 to obtain the acylhydrazine compound;

[0182] wherein, the structural formula of the acrylic acid is

[0183] The physicochemical properties and nuclear magnetic resonance spectrum data of Example 41 are:

[0184] Example 41, the chemical name is N'-β-naphthyl isopentenyl hydrazide (denoted as Compound 41): red-brown powder, melting point 125.9 - 126.5 °C, 1 1H NMR (400 MHz, DMSO) δ 9.72 (s, 1H), 8.00 (s, 1H), 7.70 (dd, J = 8.5, 4.8 Hz, 2H), 7.62 (d, J = 8.5 Hz, 1H), 7.40 - 7.30 (m, 1H), 7.19 (m, J = 8.1, 6.8, 1.2 Hz, 1H), 7.09 (dd, J = 8.8, 2.3 Hz, 1H), 6.91 (d, J = 2.3 Hz, 1H), 5.82 (t, J = 1.4 Hz, 1H), 2.11 (d, J = 1.3 Hz, 3H), 1.86 (d, J = 1.4 Hz, 3H).

[0185] Test example

[0186] In vitro antibacterial activity test:

[0187] The in vitro antibacterial activity was determined by the hyphal linear growth rate method: The test bacteria were: Fusarium oxysporum f. sp. vasinfectum (MK), Fusarium oxysporum f. sp. niveum (XK), Fusarium coeruleum (MG), Gibberella zeae (XC), Alternaria solani (FZ), Alternaria brassicae (BH), Alternaria alternata (YC), Curvularia lunata (SD), Colletotrichum gloeosporioides (PT), Fusarium oxysporum f. sp. cucumerinum (NK), Valsa mali (PF), Magnaporthe oryzae (SD), and Physalospora piricola (PL); The medium was PDA. The test solutions of Compounds 1-41 were each prepared with a 5% (v / v) aqueous DMSO solution. The determined concentrations of Compounds 1-41 in the prepared solutions were all 80 μg / mL. Each experiment was set up with three parallel groups each time and repeated three times. The test results were expressed as the average inhibition rate;

[0188] The average inhibition rates of Compounds 1-8 against the above various pathogenic bacteria are shown in Table 3:

[0189] Table 3 Average inhibition rates of Compounds 1-8 against various pathogenic bacteria (%)

[0190]

[0191]

[0192] The average inhibition rates of Compounds 9-41 against the above various pathogenic bacteria are shown in Table 4

[0193] Table 4 Average inhibition rates of Compounds 9-41 against various pathogenic bacteria (%)

[0194]

[0195]

[0196] Pot experiment against downy mildew:

[0197] Preparation of test solution: Compounds 2, 8, 11, 14, 16, 17, 22-24, 30, 35, or 40 were each dissolved in dimethyl sulfoxide (DMSO) to prepare a 160 mg / mL solution (containing 10% by mass of OP-10). Before the test, it was diluted 533 times with water to obtain the test solution (concentration: 300 μg / mL);

[0198] Test leaves: The test bacteria were Plasmopara viticola: The spore germination method on leaves was used: The spores of the test bacteria were prepared into a concentration of 10 5Suspension with the number of spores per milliliter, and the back of grape leaves was inoculated by the spraying method. The inoculated plants were first placed in an isolation chamber with high humidity and room temperature for 24 h, then transferred to a greenhouse with environmental humidity and temperature for 48 h, and finally, transferred to an environment with high humidity for 24 h. Then, the plants were transplanted to the natural environment. After the water on the surface of the plants naturally evaporated, the infected leaves were removed from the plants, and sprayed with the test solution at a concentration of 300 μg / mL. After the water on the liquid surface naturally evaporated, the petioles of the leaves were immersed in water, and then placed in an environment with high humidity for incubation for 72 h. The test effect was evaluated by comparing the percentage of the spore coverage area on the leaf surfaces of the experimental group and the control group;

[0199] Pot experiment against powdery mildew pathogens:

[0200] Preparation of the test solution: Compounds 2, 8, 11, 14, 16, 17, 22-24, 30, 35 or 40 were respectively formulated into a solution with a concentration of 160 mg / mL using dimethyl sulfoxide (DMSO) (containing 10% by mass of OP-10). Before the test, it was diluted 533 times with water to obtain the test solution (with a concentration of 300 μg / mL);

[0201] Test leaves: The test fungus was powdery mildew pathogen of melon: The method of spore germination on leaves was adopted: The specific process was basically the same as the above-mentioned pot experiment on antibacterial activity against downy mildew pathogens. The number of melon seedlings used in each test was about 30, and the melon seedlings grew in compost containing disinfected materials. The melon plants inoculated with the spore suspension of powdery mildew pathogen of melon were placed in an environment with high humidity for 24 h, and then sprayed with the test solution at a concentration of 300 μg / mL. Five days later, the antibacterial effect was evaluated by the same method as the above-mentioned pot experiment on antibacterial activity against downy mildew pathogens.

[0202] The control indexes of compounds 2, 8, 11, 14, 16, 17, 22-24, 30, 35 or 40 against grape downy mildew and powdery mildew of melon are shown in Table 5,

[0203] Table 5 Control indexes of compounds 2, 8, 11, 14, 16, 17, 22-24, 30, 35 or 40 against grape downy mildew and powdery mildew of melon*

[0204]

[0205] Note: In the table, *0 indicates that the control effect is less than 50%, 1 indicates that the control effect is 50-80%, and 2 indicates that the control effect is greater than 80%.

[0206] As can be seen from Tables 4 to 5, at a concentration of 80 μg / mL, most of the compounds showed highly efficient and broad-spectrum in vitro inhibitory activities against 13 tested plant pathogens. Some compounds showed control efficacies of over 80% against powdery mildew of melon and downy mildew of grape at a concentration of 300 ppm, and have potential uses for preparing plant antibacterial drugs, and can be used as active ingredients or synergistic ingredients of plant antibacterial drugs.

[0207] The above are only the preferred embodiments of the present invention, and do not impose any form of limitation on the present invention. It should be noted that for those of ordinary skill in the art, without departing from the principle of the present invention, several improvements and refinements can be made, and these improvements and refinements should also be regarded as the protection scope of the present invention.

Claims

1. An enoyl hydrazide compound, characterized in that: Having a structure shown in any one of Formulas 1 to 3: In Formula 1, R 1 is methyl or n-butyl, R 2 is methyl or hydrogen; In Formula 2, R is monosubstituted or disubstituted in the benzene ring, and the type of R is one or two of fluorine, chlorine, bromine, iodine, trifluoromethyl, methyl, ethyl, isopropyl and methoxy; In the formula 3, R is 2-naphthyl.

2. The enoyl hydrazide compound according to claim 1, characterized in that In Formula 1, R 1 is methyl, R 2 is methyl; or R 1 is n-butyl, R 2 is hydrogen; In the formula 2, R is 2-fluoro, 3-fluoro, 4-fluoro, 3-chloro, 4-chloro, 3-bromo, 4-bromo, 4-iodine, 3-trifluoromethyl, 4-trifluoromethyl, 2-methyl, 3-methyl, 4-methyl, 4-ethyl, 4-isopropyl, 3-methoxy, 3,4-dimethyl, 3,5-dimethyl, 2,4-difluoro, 2,5-difluoro, 3,4-difluoro, 3,5-difluoro, 2,3-dichloro, 2,4-dichloro, 2,5-dichloro, 3,4-dichloro, 3,5-dichloro, 2-fluoro-4-chloro, 2-fluoro-4-bromo, 2-chloro-4-fluoro or 3-chloro-4-fluoro.

3. The method for preparing the enoyl hydrazide compound according to claim 1 or 2, characterized in that: The following steps are involved: Carrying out a condensation reaction between an enoic acid compound and a hydrazine compound or a hydrochloride of a hydrazine compound to obtain the enoylhydrazide compound; The olefinic acid compound has a structure shown in any one of Formulas 4 to 5: In Formula 4, R 1 is methyl or n-butyl, R 2 is methyl or hydrogen; The hydrochloride of the hydrazine compound has a structure shown in any one of Formulas 6 to 8: In Formula 7, R is substituted or disubstituted, and the type of R is one or two of fluorine, chlorine, bromine, iodine, trifluoromethyl, methyl, ethyl, isopropyl and methoxy; In the formula 8, R is 2-naphthyl; The hydrazine compound has the structure shown in formula 9 to 11: In Formula 10, R is monosubstituted or disubstituted, and the type of R is one or two of fluorine, chlorine, bromine, iodine, trifluoromethyl, methyl, ethyl, isopropyl and methoxy; In the formula 11, R is 2-naphthyl.

4. The preparation method according to claim 3, characterized in that: The molar ratio of the olefinic acid compound to the hydrazine compound or the molar ratio of the olefinic acid compound to the hydrochloride of the hydrazine compound is (1.0-1.5):1.

0.

5. The preparation method according to claim 3 or 4, characterized in that: The condensation reaction is carried out under the condition of adding a condensation agent; The condensing agent includes 1-ethyl-3-dimethylaminopropylcarbodiimide hydrochloride and 1-hydroxybenzotriazole; The molar ratio of 1-ethyl-3-dimethylaminopropylcarbodiimide hydrochloride to 1-hydroxybenzotriazole is (1.0-1.5): (0.04-0.5); The molar ratio of the olefinic acid compound to 1-ethyl-3-dimethylaminopropylcarbodiimide hydrochloride is (1.0-1.5): (1.0-1.5).

6. The preparation method according to claim 5, characterized in that: The reaction medium of the condensation reaction is an organic solvent; The organic solvent is one or more of N,N-dimethylformamide, tetrahydrofuran and acetonitrile.

7. The preparation method according to claim 3, 4 or 6, characterized in that: When the olefinic acid compound and the hydrochloride of the hydrazine compound undergo a condensation reaction, the condensation reaction is also carried out under the condition of adding triethylamine; The molar ratio of the olefinic acid compound to triethylamine is (1.0-1.5): (1.0-2.0).

8. Use of the enoyl hydrazide compound according to claim 1 or 2, the enoyl hydrazide compound prepared by the preparation method according to any one of claims 3 to 7, or the enoyl hydrazide compound represented by formula 12 in plant antibacterial; In Formula 12, R 1 , R 2 , R 3 and R 4 All are hydrogen; or R 1 , R 3 and R 4 All are hydrogen, R 2 is methyl; or R 1 , R 3 and R 4 All are hydrogen, R 2 is ethyl; or R 1 , R 3 and R 4 All are hydrogen, R 2 is n-propyl; or R 1 is methyl, R 2 , R 3 and R 4 All are hydrogen; or R 1 and R 4 All are hydrogen, R 2 and R 3 All are methyl; or R 3 and R 4 All are hydrogen, R 1 and R 2 All are methyl; or R 1 is hydrogen, R 2 and R 3 All are methyl, R 4 It is 2-chloro or 2-bromo.

9. The use according to claim 8, characterized in that The pathogens in the plant antibacterial include cotton wilt pathogens, watermelon wilt pathogens, potato dry rot pathogens, wheat fusarium rust pathogens, tomato early blight pathogens, cabbage black spot pathogens, tobacco brown spot pathogens, corn curvature pathogens, apple anthracnose pathogens, pumpkin wilt pathogens, apple rot pathogens, rice blast pathogens, apple ring rot pathogens, melon powdery mildew pathogens or grape downy mildew pathogens.

10. A plant antibacterial agent, characterized in that: The invention comprises the enoyl hydrazide compound according to claim 1 or 2, the enoyl hydrazide compound prepared by the preparation method according to any one of claims 3 to 7, or the enoyl hydrazide compound shown in formula 12.

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